US4995987A - Enhancement of the efficacy of antimicrobials by the addition of anions capable of interfering with microbial electrochemical reactions - Google Patents
Enhancement of the efficacy of antimicrobials by the addition of anions capable of interfering with microbial electrochemical reactions Download PDFInfo
- Publication number
- US4995987A US4995987A US07/410,765 US41076589A US4995987A US 4995987 A US4995987 A US 4995987A US 41076589 A US41076589 A US 41076589A US 4995987 A US4995987 A US 4995987A
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- microbial
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- chlorine
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
- C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
Definitions
- the present invention relates to applications where chemical agents are utilized as antimicrobials in an aqueous medium.
- aqueous systems contain microorganisms which exhibit either aerobic or anaerobic metabolic activity.
- the presence of these microorganisms may result from natural conditions, such as would occur from the normal multiplication of microbes in aqueous environments, or from the accidental introduction of microbes, such as sulfate-reducing bacteria (SRB) found in the oil processing industry.
- SRB sulfate-reducing bacteria
- Aerobic and anaerobic microorganisms having a respiratory metabolism biochemically oxidize either organic or inorganic chemical compounds in order to obtain energy for growth and reproduction. These are enzymatically mediated chemical oxidations and must be coupled with chemical reductions in order for the reactions to continue. This process is actually a series of oxidation/reduction steps culminating in a terminal reduction reaction which balances the initial oxidation reaction.
- the terminal reduction is usually that of the reduction of O 2 to H 2 O in aerobes and may be a number of reactions in anaerobes (e.g., SO 4 .sup. ⁇ ⁇ H 2 S for some sulfate reducing bacteria, such as Desulfovibrio).
- Oxidizing and non-oxidizing antimicrobials affect microorganisms in many various modes of action which usually have little to do with inhibiting the terminal reduction reaction. It has been discovered, in accordance with the present invention, that the addition of compounds capable of competing with the compound normally used by a microorganism as its terminal electron acceptor slows the biochemical reduction process by virtue of this competition for the electrons generated by the substrate oxidations.
- a method of maintaining an oxidizing environment compatible with chlorine is disclosed in U.S. Pat. No. 3,702,298 (Zsoldos, Jr., et. al.).
- a peroxy type salt such as sodium peroxydisulfate is combined with a multi-valent catalyst such as copper or silver.
- the three step mechanism involves, (1) the oxidation of the metal to its trivalent state, (2) the reduction of the metal to its divalent state and (3) re-oxidation as in step 1.
- H 2 S is corrosive to oilfield processing equipment, hazardous to health and noxious to the olfactory senses, compounds such as chlorine, usually in the form of hypochlorite and chlorine dioxide, are utilized to eliminate the microbials. This is turn eliminates the generation of H 2 S.
- an anti-microbial compound may not affect the reduction of sulfate to H 2 S. This is due to the anti-microbial being rendered non-toxic as a result of its reaction with the H 2 S or other reduced compounds present in the system. It has been discovered in accordance with the present invention that the addition of oxidized anion compounds to the medium provides competing species for the electrons made available by the microorganism thereby slowing the reduction of sulfate to H 2 S. The lack of H 2 S renders the environment less corrosive and provides for improved anti-microbial efficacy due to the reduction of H 2 S/anti-microbial reactions.
- Oxidized anion compounds capable of acting as terminal electron acceptor substitutes for the compounds normally utilized increase anti-microbial compound efficacy against both aerobic and anaerobic microbes, especially in systems treated with oxidizing anti-microbials such as Cl 2 ,ClO 2 , BrCl, ozone, bromo and chloro substituted halogenated triazines and the like.
- Compounds acting as substitute terminal electron acceptors are chromate, dichromate, molybdate, tungstate, nitrate, nitrite, phosphate and selenate. It is well known to use these compounds for the purpose of inhibiting corrosion caused by chlorinated compositions.
- the method of operation in this instance involves the laying down of a passive oxide film on the metal surface thereby protecting it from corrosive attack by chlorine dioxide or related compounds. It is truly unexpected to find, as disclosed herein, that the compounds identified above may be added to oilfield water-floods to substantially augment the efficacy of anti-microbials such as chlorine dioxide and the like.
- the ability of Desulfovibrio to generate ATP from the substrate oxidations is impaired by the addition of an oxidized anion as a replacement for sulfate.
- the electrons generated by the substrate oxidation must be consumed by an equal rate reduction of sulfate.
- the enzyme system for reducing sulfate becomes inefficient or nonfunctional.
- the substrate oxidation step is inhibited resulting in a partial or complete shut down in the generation of ATP.
- the terminal reduction step is enzyme mediated and does not occur spontaneously. If it was spontaneous, the substitution of sulfate with an oxidized anion might not adversely affect the cell. Its energy producing function would continue unimpeded. With Desulfovibrio, the addition of the oxidized anions poisons the cell's ultimate terminal reduction enzyme system thereby shutting down the cell's energy producing system. Once in this weakened state, the cell easily falls prey to the anti-microbial compounds.
- the anions chosen for this study were chromate, dichromate, molybdate, tungsate, nitrate, phosphate and selenate.
- the antimicrobials selected were chlorine (as hypochlorite) and chlorine dioxide.
- Desulfovibrio was used as the test organism due to its prevalence in oilfield water systems and its role in generating corrosive H 2 S.
- test parameters are as follows. A medium was prepared which is suitable for supporting the growth of Desulfovibrio desulficans, a common SRB. The ingredients are:
- the various chemicals are added to this medium, and similary may be added in full scale practice, either independently or as an anion/antimicrobial combination. Strong growth on the part of Desulfovibrio is represented by increased turbidity and blackening of the medium. This is due to the production by the microbe of FeS from Fe(NH 4 ) 2 (SO 4 ) 2 . Effective anion compounds prevent S - formation and the correlating production of FeS, which ultimately inhibits Desulfovibrio growth. Test sample observation was terminated after 7 days.
- Table I provides data on the individual efficacies of various anionic and anti-microbial compounds at inhibiting Desulfovibrio growth. Effective concentration ranges vary between the compounds. The anions selenate and dichromate and the anti-microbial chlorine dioxide all show effective inhibition at 75 ppm.
- the anti-microbial endpoints representing total inhibition of Desulfovibrio growth, for the complete set of oxidant/anion combination are listed in Tables IIA & IIB.
- Tables IIA & IIB The anti-microbial endpoints, representing total inhibition of Desulfovibrio growth, for the complete set of oxidant/anion combination are listed in Tables IIA & IIB.
- the synergistic effects of various anion/oxidant combinations are evident.
- One of these combinations is ClO 2 and selenate.
- Each compound independently was effective at inhibiting growth at a concentration of 75 ppm. However, when combined, a concentration of 25 ppm of each of the individual compounds proved to be efficacious.
- Tables IIA & IIB show, selective combinations of anions/oxidants produce synergistic anti-microbial properties.
- Table III provides a summary of the test results of the individual anion and oxidant compounds and the anion/oxidant combinations.
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
______________________________________ Peptone 5.0 g Beef Extract 3.0 g Yeast Extract 0.2 g Mg SO.sub.4 1.5 g Na.sub.2 SO.sub.4 1.5 g Fe(NH.sub.4).sub.2 (SO.sub.4).sub.2 0.1 g Glucose 5.0 g Tap Water 1.0 g pH is adjusted to 7.0 ______________________________________
TABLE I __________________________________________________________________________ Efficacy of Individual Compounds (Concentration - ppm) Compound 25 30 35 40 50 75 100 150 200 250 300 350 400 500 1000 2500 5000 10000 20000 __________________________________________________________________________ Molybdate + + + + + + + + + - - - + + + + + + + + + - - - Tungstate + + + + + + + + + + + + + + + + + + + + + + + + + + Selenate + + + + + - - - - - + + + + + - - - - - Chromate + + + + - - - - - - - + + + + - - - - - - - Dichromate + + - - - - - - - - - + + - - - - - - - - - Nitrate + + + + - - + + + + - - Phosphate + + + + + - + + + + + - Hypochlorite + + + + - - - - + + + + - - - - Chlorine + + - - - - - - Dioxide + + - - - - - - Biological + Control + __________________________________________________________________________ + = Growth - = No Growth
TABLE IIA __________________________________________________________________________ Efficacy of Anion/Hypochlorite Combinations Hypochlorite Anion Anion Concentration 50 ppm 75 ppm 100 ppm ppm 25 50 75 100 200 500 25 50 75 100 2500 5000 10000 25 50 75 100 __________________________________________________________________________ Molybdate + + - - - - - - - + + - - - - - - - Tungstate + + + + + + + + + + Selenate + + - - - - + + - - - - Chromate + + - - - - - - - + + - - - - - - - Dichromate + + - - - - - - - + + - - - - - - - Nitrate - - - - - - Phosphate + + + + + + Biological + Control + __________________________________________________________________________ + = Growth - = No Growth
TABLE IIB __________________________________________________________________________ Efficacy of Anion/Chlorine Dioxide Combinations Chlorine Dioxide Anion Anion Concentration 25 ppm 50 ppm 75 ppm ppm 10 25 50 75 10 25 50 75 100 200 300 2500 5000 10000 100 200 300 2500 5000 10000 __________________________________________________________________________ Molybdate + - - + - - + - - + - - Tungstate + + + + + + + + + + + + + + + + + + + + + + + + Selenate + - - - + + - - + - - - + + - - Chromate + + + + - - + + + + - - Dichromate + + + + - - + + + + - - Nitrate - - - + - - - - - - - - Phosphate + + + + + + + + + + + + __________________________________________________________________________
TABLE III __________________________________________________________________________ Summary of Oxidant/Anion Efficacy Individual HOCl ClO.sub.2 Anion Concentration 50 ppm 75 ppm 100 ppm 25 ppm 50 ppm __________________________________________________________________________ Molybdate 300 ppm 200 ppm 25 ppm 25 ppm 25 ppm 25 ppm Tungstate 1,000 ppm NE NT NT NE NE Selenate 75 ppm NE 25 ppm 50 ppm 25 ppm 50 ppm Chromate 150 ppm 100 ppm 25 ppm 25 ppm NE 25 ppm Dichromate 75 ppm 75 ppm 25 ppm 25 ppm NE 25 ppm Nitrate 10,000 ppm NT 2500 ppm NT NT 2500 ppm Phosphate 20,000 ppm NT NE NT NT NE Hypochlorite 200 ppm Chlorine 75 ppm Dioxide __________________________________________________________________________ NE: Not Efficacious NT: Not Tested
Claims (12)
Priority Applications (1)
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US07/410,765 US4995987A (en) | 1989-09-21 | 1989-09-21 | Enhancement of the efficacy of antimicrobials by the addition of anions capable of interfering with microbial electrochemical reactions |
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US07/410,765 US4995987A (en) | 1989-09-21 | 1989-09-21 | Enhancement of the efficacy of antimicrobials by the addition of anions capable of interfering with microbial electrochemical reactions |
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US07/410,765 Expired - Lifetime US4995987A (en) | 1989-09-21 | 1989-09-21 | Enhancement of the efficacy of antimicrobials by the addition of anions capable of interfering with microbial electrochemical reactions |
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Cited By (41)
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US5459125A (en) * | 1993-07-22 | 1995-10-17 | Bj Services Company | Corrosion inhibitor composition and method of use |
EP0726357A1 (en) * | 1995-02-07 | 1996-08-14 | Betz Laboratories Inc. | Inhibiting anaerobic production of volatile fatty acids and hydrogen by bacteria |
US5984993A (en) * | 1998-03-20 | 1999-11-16 | Vulcan Materials Company | Method and composition for odor control |
FR2792500A1 (en) * | 1999-04-23 | 2000-10-27 | Int Redox Dev | Oxidizing compositions containing metal ions, hydrogen peroxide, acetic or propionic acid and their peracids, and a stabilizer, for pharmaceutical and hygiene use, and to clean and scour metallic and non-metallic surfaces |
EP1095185A1 (en) * | 1998-05-12 | 2001-05-02 | Great Lakes Chemical Corporation | Process for controlling odor in paper and paperboard |
US20010004461A1 (en) * | 1998-06-01 | 2001-06-21 | Moore Robert M. | Continuous processes for preparing concentrated aqueous liquid biocidal compositions |
US6299909B1 (en) | 1998-06-01 | 2001-10-09 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation |
US6348219B1 (en) | 1998-06-01 | 2002-02-19 | Albemarle Corporation | Processes for preparing concentrated aqueous liquid biocidal compositions |
US6352725B1 (en) | 1998-06-01 | 2002-03-05 | Albemarle Corporation | Continuous processes for preparing concentrated aqueous liquid biocidal composition |
US6375991B1 (en) | 2000-09-08 | 2002-04-23 | Albemarle Corporation | Production of concentrated biocidal solutions |
US6506418B1 (en) | 1999-09-24 | 2003-01-14 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation |
US6511682B1 (en) | 1998-06-01 | 2003-01-28 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation |
US20030113402A1 (en) * | 2001-06-28 | 2003-06-19 | Howarth Jonathan N. | Microbiological control in animal processing |
FR2835702A1 (en) * | 2002-02-12 | 2003-08-15 | Dominique Mercier | Disinfectant composition useful in the disinfection of water comprises a mixture of sodium hypochlorite and sodium monophosphate |
US20030211210A1 (en) * | 2001-06-28 | 2003-11-13 | Howarth Jonathan N. | Microbiological control in poultry processing |
US6652889B2 (en) | 1998-06-01 | 2003-11-25 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation and use |
US20040082632A1 (en) * | 2000-01-18 | 2004-04-29 | Howarth Jonathan N. | Methods for microbiological control in aqueous systems |
US20040120853A1 (en) * | 2002-12-20 | 2004-06-24 | Carpenter Joel F. | Biocidal control in recovery of oil by water injection |
US20040231982A1 (en) * | 2003-03-04 | 2004-11-25 | Contos Michael A. | Treating an electrocoat system with a biosurfactant |
US20040231988A1 (en) * | 2003-03-04 | 2004-11-25 | Pillar Lonnie L. | Detecting micro-organisms in an electrocoating process |
US20040265446A1 (en) * | 2003-06-24 | 2004-12-30 | Mcnaughton James L. | Microbiocidal control in the processing of poultry |
US20040265445A1 (en) * | 2003-06-24 | 2004-12-30 | Liimatta Eric W. | Microbiocidal control in the processing of poultry |
US20050010321A1 (en) * | 2003-03-04 | 2005-01-13 | Contos Michael A. | Electrocoat management system |
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US7087251B2 (en) | 1998-06-01 | 2006-08-08 | Albemarle Corporation | Control of biofilm |
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US8765652B2 (en) | 2004-03-05 | 2014-07-01 | Gen-Probe Incorporated | Method of making a formulation for deactivating nucleic acids |
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